Selective thermal atomic layer etching
The disclosed and claimed subject matter relates to selective thermal atomic layer etching with a novel series of halogen-free organic acids cycled with an oxidant as a co-reactant to etch metals.
1 . A thermal atomic layer etching process performed in a reactor for selectively etching a metal substrate comprising the steps of:
Step 1 comprising sequentially performing:
Step 1A comprising exposing a metal surface to an oxidizing vapor comprising one or more of water vapor, oxygen, ozone, nitrous oxide, nitric oxide, hydrogen peroxide, oxygen plasma, and combinations thereof, and
Step 1B comprising purging the oxidizing vapor with an inert gas; and
Step 2 comprising sequentially performing:
Step 2A comprising exposing the metal surface to one or more halogen-free organic acid volatizer, and
Step 2B comprising purging the one or more halogen-free organic acid volatizer with an inert gas;
wherein one cycle of the process is determined by the formula (Step 1) n +(Step 2) m , wherein n and m are each independently=1-20, and wherein the Step 2A one or more halogen-free organic acid volatizer is heated to and held at from about 50° C. to about 100° C.
2 . The process of claim 1 , wherein the process comprises about 20 to about 2200 cycles.
3 . The process of claim 1 , wherein the process comprises selectively etching one or more of copper, cobalt, molybdenum and tungsten.
4 . The process of claim 1 , wherein the process comprises selectively etching copper preferentially instead of one or more of nickel, platinum, ruthenium, zirconium oxide and SiO 2 .
5 . The process of claim 1 , wherein the process comprises selectively etching cobalt preferentially instead of one or more of nickel, platinum, ruthenium, zirconium oxide and SiO 2 .
6 . The process of claim 1 , wherein the process comprises selectively etching molybdenum preferentially instead of one or more of nickel, platinum, ruthenium, zirconium oxide and SiO 2 .
7 . The process of claim 1 , wherein the process comprises selectively etching tungsten preferentially instead of one or more of nickel, platinum, ruthenium, zirconium oxide and SiO 2 .
8 . The process of claim 1 , wherein the reactor comprises an outer heater heated to a temperature of about 100° C. to about 300° C. and an inner heater heated to a temperature of about 100° C. to about 350° C.
9 . The process of claim 1 , wherein the Step 1A oxidizing vapor comprises one or more of water vapor, oxygen, ozone and hydrogen peroxide.
10 . The process of claim 1 , wherein the Step 1A oxidizing vapor comprises water vapor and one or more of oxygen and ozone.
11 . The process of claim 1 , wherein the Step 2A one or more halogen-free organic acid volatizer comprises one or more of propionic acid, isobutyric acid, pivalic acid, acetic acid, butanoic acid, acrylic acid, methacrylic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, 3-butenoic acid, cyclopropanecarboxylic acid, pentanoic acid, (2E)-but-2-enoic acid, (Z)-2-butenoic acid and combinations thereof.
12 . The process of claim 1 , wherein the Step 2A one or more halogen-free organic acid volatizer comprises one or more of propionic acid, isobutyric acid, pivalic acid and combinations thereof.
13 . The process of claim 1 , wherein the Step 2A one or more halogen-free organic acid volatizer comprises propionic acid.
14 . The process of claim 1 , wherein the Step 2A one or more halogen-free organic acid volatizer comprises isobutyric acid.
15 . The process of claim 1 , wherein the Step 2A one or more halogen-free organic acid volatizer comprises pivalic acid.
16 . The process of claim 1 , wherein the Step 2A one or more halogen-free organic acid volatizer comprises two or more of propionic acid, isobutyric acid and pivalic acid.
17 . A thermal atomic layer etching process performed in a reactor for selectively etching a metal substrate comprising the steps of:
Step 1 comprising sequentially performing:
Step 1A comprising exposing a metal surface to an oxidizing vapor comprising one or more of water vapor, oxygen, ozone, nitrous oxide, nitric oxide, hydrogen peroxide, oxygen plasma, and combinations thereof, and
Step 1B comprising purging the oxidizing vapor with an inert gas; and
Step 2 comprising sequentially performing:
Step 2A comprising exposing the metal surface to one or more halogen-free organic acid volatizer, and
Step 2B comprising purging the one or more halogen-free organic acid volatizer with an inert gas;
wherein one cycle of the process is determined by the formula (Step 1) n+ (Step 2) m, wherein n and m are each independently=1-20 and wherein the Step 2A one or more halogen-free organic acid volatizer comprises one or more of propionic acid, isobutyric acid, pivalic acid and combinations thereof.
18 . The process of claim 17 , wherein the process comprises about 20 to about 2200 cycles.
19 . The process of claim 17 , wherein the process comprises selectively etching one or more of copper, cobalt, molybdenum and tungsten.
20 . The process of claim 17 , wherein the process comprises selectively etching copper preferentially instead of one or more of nickel, platinum, ruthenium, zirconium oxide and SiO 2 .
21 . The process of claim 17 , wherein the process comprises selectively etching cobalt preferentially instead of one or more of nickel, platinum, ruthenium, zirconium oxide and SiO 2 .
22 . The process of claim 17 , wherein the process comprises selectively etching molybdenum preferentially instead of one or more of nickel, platinum, ruthenium, zirconium oxide and SiO 2 .
23 . The process of claim 17 , wherein the process comprises selectively etching tungsten preferentially instead of one or more of nickel, platinum, ruthenium, zirconium oxide and SiO 2 .
24 . The process of claim 17 , wherein the reactor comprises an outer heater heated to a temperature of about 100° C. to about 300° C. and an inner heater heated to a temperature of about 100° C. to about 350° C.
25 . The process of claim 17 , wherein the Step 1A oxidizing vapor comprises one or more of water vapor, oxygen, ozone and hydrogen peroxide.
26 . The process of claim 17 , wherein the Step 1A oxidizing vapor comprises water vapor and one or more of oxygen and ozone.
27 . The process of claim 17 , wherein the Step 2A one or more halogen-free organic acid volatizer comprises propionic acid.
28 . The process of claim 17 , wherein the Step 2A one or more halogen-free organic acid volatizer comprises isobutyric acid.
29 . The process of claim 17 , wherein the Step 2A one or more halogen-free organic acid volatizer comprises pivalic acid.
30 . The process of claim 17 , wherein the Step 2A one or more halogen-free organic acid volatizer comprises two or more of propionic acid, isobutyric acid and pivalic acid.
31 . The process of claim 17 , wherein the Step 2A one or more halogen-free organic acid volatizer is heated to and held at from about 50° C. to about 100° C.